Composition of matter tailoring: system ia

ABSTRACT

The present invention relates to tailored materials, particularly metals and alloys, and methods of making such materials. The new compositions of matter exhibit long-range ordering and unique electronic character.

RELATED APPLICATIONS

This application is a Continuation of U.S. application Ser. No.12/609,044, filed Oct. 30, 2009, which claims the benefit of U.S.Provisional Application No. 61/109,751, filed Oct. 30, 2008 and U.S.Provisional Application No. 61/165,689, filed on Apr. 1, 2009. Theentire teachings of the above applications are incorporated herein byreference.

BACKGROUND OF THE INVENTION

Tailoring a variety of materials has been described in U.S. Pat. Nos.6,572,792 and 7,238,297, entitled “COMPOSITION OF MATTER TAILORING:SYSTEM I” and U.S. Ser. No. 11/063,694 entitled “COMPOSITION OF MATTERTAILORING: SYSTEM II”, filed Feb. 23, 2005, each by Christopher Nagel,the contents of which are incorporated herein by reference. In themethods described in the prior patents, carbon is added to the materialin an iterative heating cycle and the products produced by the methodspossess modified electronic structures. A disadvantage of these methodsis that the products obtained thereby are characterized by carboncontaminants, often at levels of saturation or above.

SUMMARY OF THE INVENTION

The present invention relates to the unexpected discovery that theaddition of carbon is not essential to tailoring materials. In fact, thediscovery was made as a result of an experiment of the previouslydescribed process where the induction furnace failed to bring thematerial up to the targeted initial temperature and prior to the plannedaddition of carbon. It was then appreciated that tailoring can beachieved even in the absence of carbon addition, resulting in productsthat are “essentially carbon free.” This serendipitous discovery gaverise to the inventions described and claimed herein.

The materials that can be tailored in accordance with the presentinvention include matter comprised of ‘p’, ‘d’, and/or ‘f’ atomicorbitals and include but are not limited to metals. The tailoredmaterials produced in accordance with the invention are defined by, canbe distinguished and/or are characterized by a change in one or moreenergy, electronic properties, physical properties, and the like. X-rayfluorescence spectroscopy is one method of detecting and distinguishingtailored materials. Changes in properties can be made and/or controlledto be transient, fixed, or adjustable (temporarily permanent) andinclude properties such as mechanical, electrical, chemical, thermal,engineering, and physical properties, as well structural character ofthe composition of matter (e.g., alignment, orientation, order,anisotropy, and the like).

The present invention includes manufactured metals and alloys that areessentially carbon-free and are characterized by the x-ray fluorescencespectrometry plots and elemental abundance tables (obtained from x-rayfluorescence analysis) such as those described herein.

The present invention relates to a method of processing, or tailoring, amaterial, such as a metal or an alloy of metals, the improvementcomprising tailoring in the absence of carbon. The method generallyrequires subjecting a material to a symmetrically or asymmetricallyoscillating electromagnetic field in the absence of a step of addingcarbon. This method can be achieved by subjecting the material to aniterative cycling between two or more temperatures (which can be aconsequence of the oscillating field). In one embodiment, the methodcomprises the steps of:

-   -   (A) adding and, optionally, melting a material in a reactor;    -   (B) subjecting the material to an iterative cycling of        increasing and decreasing the temperature of the material, such        as by varying the temperature of the material between at least        two temperatures over one or more cycles, in the substantial        absence of carbon, optionally in the presence of an inert gas        flow through the material;    -   (C) optionally repeating step (B) at the same or different        temperatures, one of said temperatures is preferably greater        than at least one or both of the temperatures of step (B); and    -   (D) optionally, cooling the material obtained from step (B)        or (C) and selecting a tailored material.

The incremental increasing can be, for example, where the moltenmaterial is raised and decreased between two set temperatures (T1 andT2). Alternatively, the temperatures of each cycle can be changed(increased or decreased). For example, the molten material can be raisedto a temperature T1, decreased to a temperature T2, raised to atemperature T3 (where T3>T1>T2), decreased to a temperature T4 (whereT3>T1>/=/<T4>T2), and so on, thereby, incrementally increasing thetemperatures of each cycle.

The method of the invention can also include an optional holding stepwhereby the material is held at a selected temperature for a selectedperiod of time, optionally in the presence of gas addition.

Optionally, the processes of the invention further comprise at least one(e.g., any 2, 3, 4, 5, 6, 7, 8 or 9) of the following steps:

-   -   (a) the gas or gaseous addition (e.g., nitrogen, hydrogen,        and/or noble gas) is added to the material through a lance set        at a level above the liquid level;    -   (b) at least one of the gases or gaseous additions comprises a        gas mixture;    -   (c) at least one of the gases has been exposed to radiation;    -   (d) current, e.g., AC or DC current, is added to the material in        a further step or during one or more of the above steps;    -   (e) during the cooling step, a gas is added to the material;        and/or    -   (f) during the cooling step, the material is quenched with water        wherein the water is not stirred;    -   (g) at least one form of radiation has been filtered;    -   (h) the material is exposed to radiation in a further step or        during one or more of the above steps; and/or    -   (i) varying the reactor power (e.g., above normal holding power)        between two power levels over ½, one or more cycles.

In another embodiment, the present invention is a method of processingcopper, or other metal or alloy comprising subjecting copper, or othermaterial, metal or alloy to an iterative energy cycling process in theabsence of carbon under conditions suitable to achieve tailoring andtesting the product of the process for tailoring and selecting atailored copper.

In other embodiments, the oscillating magnetic field can be achieved bydelivering energy in a form other than heat, as described in more detailbelow.

Advantages of the present invention include a method of processingmetals into new compositions of matter and producing and characterizingcompositions of matter with altered physical and/or electricalproperties without the need to add a carbon source.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A-1H illustrate the furnace power cycling and bath temperatureduring the experiment.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to new compositions of matter, referred toherein as “manufactured” materials, metals or alloys of metals. A“manufactured” metal or alloy is a metal or alloy which exhibits achange in electronic structure, such as that seen in a fluid XRFspectrum. The American Heritage College Dictionary, Third Editiondefines “fluid” as changing or tending to change.

Metals of the present invention are generally p, d, or f block metals.Metals include transition metals such as Group 3 metals (e.g., scandium,yttrium, lanthanum), Group 4 metals (e.g., titanium, zirconium,hafnium), Group 5 metals (vanadium, niobium, tantalum), Group 6 metals(e.g., chromium, molybdenum, tungsten), Group 7 metals (e.g., manganese,technetium, rhenium), Group 8 metals (e.g., iron, ruthenium, osmium),Group 9 metals (e.g., cobalt, rhodium, iridium), Group 10 metals(nickel, palladium, platinum), Group 11 metals (e.g., copper, silver,gold), and Group 12 metals (e.g., zinc, cadmium, mercury). Metals of thepresent invention also include alkali metals (e.g., lithium, sodium,potassium, rubidium, and cesium) and alkaline earth metals (e.g.,beryllium, magnesium, calcium, strontium, barium). Additional metalsinclude lanthanides, aluminum, gallium, indium, tin, lead, boron,germanium, arsenic, antimony, tellurium, bismuth, thallium, polonium,astatine, and silicon.

The present invention also includes alloys of metals. Alloys aretypically mixtures of metals. Alloys of the present invention can beformed, for example, by melting together two or more of the metalslisted above. Preferred alloys include those comprised of copper, gold,and silver; tin, zinc, and lead; tin, sodium, magnesium, and potassium;iron, vanadium, chromium, and manganese; nickel, tantalum, hafnium, andtungsten; copper and ruthenium; nickel and ruthenium; cobalt andruthenium; cobalt, vanadium and ruthenium; and nickel, vanadium andruthenium. Materials other than metals can also be tailored inaccordance to the invention.

The present invention also includes alloys of metals or mixtures ofother materials. Alloys are typically mixtures of metals. Alloys of thepresent invention can be formed, for example, by melting together two ormore of the metals listed above.

A cycle of the present invention includes a period of time where thetemperature of the material is varied between two distinct temperatures(T1 to T2, wherein T1<T2).

Over a period of time, a cycle involves varying the temperatureincluding a period of raising (or increasing) the temperature of thematerial and a period when the temperature decreases (either passively,such as by heat transfer to the surrounding environment, or actively,such as by mechanical means), in any order. Inert gas can be addedduring the entire cycle or part of the cycle.

The temperatures selected for each cycle is preferably increased suchthat T1 of cycle 2 is greater than T1 of cycle 1 and T2 of cycle 2 isgreater than T2 of cycle 1, and so on. Each cycle between to twotemperatures, T1 and T2, can include two or more iterations.

An iterative cycle process is a process comprising two or more cycles,whereby one or more of the cycles are carried out between two or moretemperatures. For example, in Example 1, the induction furnace was setto bring the temperature of the reactor up to 2462° F. at a rate to notexceed 150° F./hr, controlled by a feedback loop. Because ofinsufficient insulation wrapping, the temperature in the inductionfurnace entered into an iterative cycling heating process that reached afinal temperature of 2386° F. The material subjected to the processunexpectedly was tailored.

As can be seen from the experiment, cycles of the present invention canvary in duration and can be symmetric or asymmetric. In a symmetriccycle, the period of increasing the metal or alloy temperature is equalto the period of decreasing the metal or alloy temperature. In anasymmetric cycle, the period of increasing the metal or alloytemperature is different than the period of decreasing the metal oralloy temperature. For an asymmetric cycle, the period of increasing themetal or alloy temperature can be longer than or shorter than the periodof decreasing the metal or alloy temperature.

The time period is, in part, dictated by the rate of heating and coolingwhich is practical by the equipment (e.g., induction furnace) used, thematerial selected and the mass of material being processed. The timeperiod of each sweep of an iteration or cycle can be selected to producesets of energy patterns.

A cycle can also include, or be interrupted or ended with, a holdingstep. Thus, the material can be held at an energy level (as measured,for example, by the temperature or degree of carbon saturation) for aselected period of time. The holding period can be several minutes toseveral hours or more. For example, the material can be held for 60minutes or 5 minutes. More than one hold step can be incorporated intothe process and can be included in an iteration of steps.

The number of cycles in a step is generally an integer or half-integervalue. For example, the number of cycles in a step can be one or more,one to forty, or one to twenty. The number of cycles can be 1, 2, 3, 4,5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23,24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, or 40.Alternatively, the number of cycles in a step can be 0.5, 1.5, 2.5, 3.5,4.5, 5.5, 6.5, 7.5, 8.5, 9.5, 10.5, 11.5, 12.5, 13.5, 14.5, 15.5, 16.5,17.5, 18.5, 19.5, 20.5, 21.5, 22.5, 23.5, 24.5, 25.5, 26.5, 27.5, 28.5,29.5, or 30.5. In a step comprising a half-integer or a non-integerquantity of cycles, either heating or cooling can occur first.

In one embodiment, the process is preferably conducted in a moltenstate. Cycling temperatures for tailoring molten metals can be typicallybetween about 900° F. to about 3000° F. For example, the temperature canbe about 1932° F. to about 2467° F. for copper; about 2368° F. to about2855° F. for nickel; about 2358° F. to about 2805° F. for cobalt; and soon.

Gas, such as nitrogen, hydrogen or a noble gas, can be added during acycle, except where it is specified that gas addition is ceased prior tothat cycle. The gas provides a third body effect for the reactionfacilitating energy exchange. For example, hydrogen, helium, nitrogen,neon, argon, krypton, xenon and carbon monoxide can be added. In apreferred embodiment, the gas is added as a mixture. A preferred mixturecomprises argon, helium, neon and/or krypton. Preferably, at least 50%,more preferably at least 80% such as at least 90% by volume argon,helium or hydrogen is present in the mixture. Particularly preferredmixtures, by volume, include (1) 93% argon, 5% helium and 2% neon; (2)92% argon, 5% helium and 3% neon; (3) 95% argon and 5% helium or neon;(4) 95% helium and 5% krypton; (5) 95% nitrogen and 5% helium; (6) 97%helium and 3% neon (optionally trace amounts of krypton); (7) 97% argonand 3% neon; (8) 60% argon and 40% helium (optionally trace amounts ofneon, hydrogen and/or krypton); (9) 49.5% hydrogen, 49.5% helium and 1%neon. In selecting the specific combination and concentrations of thegases, the following factors should be considered: emission profile,Hodge spectral character and required momentum/energy exchange.

In each embodiment, the gas can be added at various rates. In general,the gas is added in terms of the resulting agitation on the material andexchange with the material. As such, the gas can be added at a low rate,resulting in low agitation/exchange; at a modest, moderate or high orvigorous rate. The gases can be mixed prior to adding or addedindividually. Using conventional fluid dynamic scaling models andassuming a crucible size of 3.75 inches I.D., with a 14.5 inch height,holding 20 lbs of cobalt, examples of low agitation can be achieved byadding about 0.25 SLPM; modest agitation can be achieved by addingbetween about 1.25 SLPM; moderate agitation can be achieved by addingbetween about 2.5 SLPM and high agitation can be achieved agitation byadding between about 5.0 SLPM. Selecting low agitation generally resultsin clearly defined bubbles in a quiescent bath. High agitation generallyresults in a turbulent well-mixed bath. Modest and moderate agitationrates enables mixing and exchange to be adjusted between these extremes.In some instances, the rate of addition can begin at one level and bechanged during the step to a different level (e.g., from a low rate to avigorous rate). In general, it is desirable to add the gas at a rate ofexcess to assist in controlling the reaction and ensuring that ratelimiting steps are not associated with mass transfer diffusion. Flowrates for a crucible size of 8.875 inches, with a 16.5 inch height,holding 100 lbs of copper can be determined using standard scalingtechniques based on bubble size and residence time distributions toachieve similar transport phenomena.

The gas can be added to the material either below or above (includingacross) the surface level of the material. When the gas is added belowthe surface level, it can be added via injection ports from the bottomor sides of the reactor. However, it is often preferred to add the gasvia a lance. The lance can be positioned to provide gas entry below thesurface level, e.g. at the bottom of the reactor, midpoint or near thesurface of the material. When the lance is to be submerged, it is oftendesirable to position the lance prior to or during the initial chargingof the reactor with the material (e.g., as the reactor is being packedwith metal pellets). Where the lance is not submerged, the lance can beplaced to direct the gas across the surface of the material or toward atthe surface. Where the gas is directed toward the material, the gas canbe directed at a force that creates an indentation in the surface. Thelance can be placed along the centerline of the reactor. However, it isoften desirable to place the lance off center, e.g., at about two thirdsradius point as measured from the center. Lance placement involvesconsideration of mass/energy transfer, interaction of multiple lances,and physicochemical and photochemical characteristics of the reactantsbeing added.

The material can be subjected or exposed to the gas either during theentire process or a cycle or series of cycles or alternating cycles,during the cooling step or thereafter as a post treatment step.

In one embodiment, the gas is exposed to radiation. The exposure can beapplied in a continuous or batch mode. For example, the radiation sourcecan be applied as the gas moves through a conduit for the gas source tothe reactor. The conduit is preferably not opaque and is more preferablytranslucent or transparent. The radiation can be applied in an open orclosed system. A closed system entails exposing the gas to the specifiedradiation in the substantial absence of other radiation sources (e.g.,visible light, magnetic fields above background). This can be easilyaccomplished by building a black box surrounding a segment of theconduit and placing the radiation source(s) within the black box. Anopen system can also be employed where the radiation source(s) are notshielded from ambient light.

In yet other embodiments, the material itself can be subjected toradiation (an additional form of applying an oscillating electromagneticfield), either in lieu of, during or after the processes describedherein. For example, a tailored metal can be subjected to radiation tofurther modify the properties of the metal.

The radiation sources can be selected to provide a broad range ofemitted wavelengths. For example, the radiation can range from infraredto ultraviolet wavelengths. In one embodiment, examples of preferredradiation sources emit into the range of 160 nm to 1000 nm; in anotherembodiment, examples of preferred radiation sources emit and into therange of 180 nm to 1100 nm; and in a more preferred embodiment examplesof preferred radiation sources emit into the range of 400 nm to 700 nm.The radiation can be conveniently supplied by short arc lamps, highintensity discharge lamps, pencil lamps, lasers, light emitting diodes,incandescent, fluorescent, and/or halogens for example. Examples ofsuitable high intensity discharge lamps include mercury vapor, sodiumvapor and/or metal halide. Short arc lamps include mercury, xenon ormercury-xenon lamps. Pencil lamps include neon, argon, krypton, xenon,short wave ultraviolet, long wave ultraviolet, mercury, mercury/argon,mercury/neon, and the like. The radiation can also include (or exclude),incandescent or fluorescent light and/or natural sources of light, suchas electromagnetic radiation emitted by celestial bodies.

The radiation sources can optionally be used in combination with lightshields or wavelength filters. Examples of suitable shields and filterscan be obtained from UVP, Inc. (Upland, Calif.). The filters and shieldscan direct or modify the emission output. Examples of UVP Pen-RayFilters include the G-275 filter which absorbs visible light whiletransmitting ultraviolet at 254 nm and the G-278 filter which convertsshortwave radiation to longwave radiation at 365 nm. Pen-Ray Shieldsinclude Shield A which has a 0.04 inch ID hole for point-like source,Shield B which has a 0.31×0.63 inch window, and Shield C which has a0.19×1.5 inch window. Filters and shields can also be obtained fromNewport Corp. (Irvine, Calif.). The Newport 6041 Short Wave Filterabsorbs visible lines; the 6042 Long Wave Conversion Filter attenuatesthe 253.7 nm Hg line and fluoresces from 300-400 nm; and the 6057 GlassSafety Filter absorbs the 253.7 nm Hg line and attenuates the 312.6 nmline. The Aperture Shields offered by Newport include the 6038 PinholeShield which has a 0.040 inch (1 mm) diameter, the 6039 Small ApertureShield which has a 0.313×0.375 inch window and the 6040 Large ApertureShield with a 0.188×1.50 inch window. Filters and shields can also beobtained from Edmund Industrial Optics Inc. (Barrington, N.J.). TheEdmund UV Light Shield A has a 1 mm inner diameter drilled hole; ShieldB has a 7.9 mm×15.9 mm aperture; and Shield C has a 4.8 mm×38.2 mmaperture.

The orientation of the lamp can also impact upon the result obtained.Thus, in the embodiment where a gas is subjected to a radiation source,the radiation source can be fixed to direct the radiation directlytowards, perpendicular, away or parallel to the conduit directing thegas, or its entry or exit point. The gases can be those discussed aboveor other gases, such as air or oxygen. The radiation source can bepositioned horizontally, vertically and/or at an angle above, belowacross from the conduit. For example, the base of a pencil lamp (orother radiation source) can be set at the same height of the conduit andthe tip of the lamp directed or pointed toward the conduit.Alternatively, the base of the pencil lamp (or other radiation source)can be set at the height of the conduit and the lamp directed at a 30°(40°, 45°, 50°, 55°, 60°, or 90°) angle above (below) the conduit.Alternatively, the base of the pencil lamp can be fixed above or belowthe level of the conduit. The tip of the pencil lamp can be pointed upor down, in the direction of the gas flow or against the gas flow or atanother angle with respect to any of the above. Further, more than oneof the same or different pencil lamps alone or in combination with otherradiation sources can be used, set at the same or different heights,orientations and angles. The lamps can be presented in alternativeorders (first xenon, then mercury or vice versa).

In an embodiment wherein the material to be treated is subjected to theradiation source, similar positions can be achieved as above withrespect to the gas conduit. The radiation source can be fixed to directthe radiation directly towards, perpendicular, away or parallel to thematerial. The radiation source can be positioned horizontally,vertically and/or at an angle above, below across from the material. Asabove, the base of a pencil lamp (or other radiation source) can be setat the same height of the material and the tip of the lamp directed orpointed toward the material. Alternatively, the base of the pencil lamp(or other radiation source) can be set at the height of the material andthe lamp directed at a 30° (40°, 45°, 50°, 55°, 60°, or 90°) angle above(below) the material. Alternatively, the base of the pencil lamp can befixed above or below the level of the material. The tip of the pencillamp can be pointed up or down, in the direction of the gas flow oragainst the gas flow or at another angle with respect to any of theabove. Further, more than one of the same or different pencil lampsalone or in combination with other radiation sources can be used, set atthe same or different heights, orientations and angles.

In a preferred embodiment, the radiation source is a high intensitydischarge lamp positioned to direct the radiation towards the material.The high intensity discharge lamp is combined with one or more pencillamps positioned proximal to the high intensity discharge lamp. Often,high intensity discharge lamps are equipped with a hood or reflector todirect the radiation. In some instances, one or more pencil lamps can beplaced inside and/or behind the reflector.

Further, the distance between the radiation source and the materialand/or gas conduit can impact the results achieved. For example, thelamps can be placed between about 5 and 100 cm or more from the conduitand/or material. In other embodiments, the distance between theradiation source and the material and/or gas conduit can be betweenabout 100 cm and 5 meters or more.

In other instances, the radiation can be filtered. Filters, such ascolored glass filters, available from photography supply shops, forexample, can be used. In yet other embodiments, the filter can be othermaterials, such as water, gas (air or other gas), a manufactured ortailored material, such as those materials described or made herein, ora material of selected density, chemical make-up, properties orstructure. In one embodiment, the filter can be placed between theradiation source(s) and the target metal or alloy or gas used in themethod. Filters can also be called “forcing functions.” Forcingfunctions can be used in conjunction with electromagnetic radiationsources to induce or affect a change in a material. In addition, gasesmay be injected into apparatus containing a forcing function to modifythe performance of the assembly.

In one embodiment, the radiation source has an environment which isdifferent from that of the material. This can be accomplished bydirecting a gas flow into the lamp environment. Where the radiationsource is a pencil lamp within a box to radiate a gas, this can beaccomplished by direct gas flow into the box. In other embodiments, theradiation source can be a short arc lamp or a short arc lamp assembly.In such embodiments, the gas can be introduced into the reflectorproximate to the lamp. The gas includes those gases discussed above.

The radiation can be applied continuously or discontinuously (e.g.pulsed or toggled) and its intensity can be modulated. Where theradiation is applied continuously, the radiation can begin prior tointroduction of the gas into the conduit or after. It can be applied forthe duration of a cycle or series of cycles. Where the radiation ispulsed, the length of each pulse can be the same or different.Generally, the radiation is applied to induce change, altering the gasor target materials prior to their introduction into the reactor. Thisis conveniently accomplished by controlling the lamps with a computer.The factors to be considered in radiation source placement, exposure andsequence include the desired wavelength, intensity, and energycharacteristics, the angle of incidence, and the harmonic profile to beinjected into the targeted material (e.g. gas, metal, tailored metal,radiated gas and the like).

In some instances, the radiation source and/or pencil lamp(s) and/orfilters and/or target material or gas are advantageously cooled. Forexample, where a high intensity discharge lamp is used in combinationwith a pencil lamp(s), it may be advantageous to cool the pencil lamp toprevent damage. Alternatively, where a short arc lamp is used incombination with pencil lamps and/or glass filters it may beadvantageous to cool the pencil lamps to prevent damage as well as theglass filter to prevent breakage.

Other sources of energy can be used to apply an oscillatingelectromagnetic field and tailor the materials of the invention. Forexample, DC current can be applied continuously or the amperage varied,for example between 0-300 amps, such as 0-150 amps. AC current can beapplied continuously or varied, e.g., in a wave pattern, such as asinusoidal wave, square wave, or triangle wave pattern of a selectedfrequency and amplitude. Typically, 10 volts, peak to peak, is used at0-3.5 MHz, 0-28 MHz, or 0-50 MHz. In other embodiments, the peak to peakvoltage was less that about 15 vdc, 10 vdc, 8 vdc, 7.2 vdc, 5 vdc, 1.7vdc, and 1 vdc. A frequency generator can be used. In one embodiment,electrodes can be placed in the reactor, such as below the surface ofthe material, and current applied. As with the radiation discussedabove, the current can be applied to coincide with a cycle or series ofcycles or during all or a part of a single step of the process. Oftenthe power supply is turned on prior to attachment to the electrodes toavoid any power surge impacts.

Methods of the present invention are carried out in a suitable reactor.Suitable reactors are selected depending on the amount of metal or alloyto be processed, mode of heating, extent of heating (temperature)required, and the like. A preferred reactor in the present method is aninduction furnace reactor, which is capable of operating in a frequencyrange of 0 kHz to about 10,000 kHz, 0 kHz to about 3,000 kHz, or 0 kHzto about 1,000 kHz. Reactors operating at lower frequencies aredesirable for larger metal charges, such that a reactor operating at0-3,000 kHz is generally suitable for 20 pound metal charges and areactor operating at 0-1,000 kHz is generally suitable for 5000 poundmetal charges.

Typically, reactors of the present method are lined with a suitablecrucible. Crucibles are selected, in part, based on the amount of metalor alloy to be heated and the temperature of the method. Cruciblesselected for the present method typically have a capacity from aboutfive pounds to about five tons. One preferred crucible is comprised of89.07% Al₂O₃, 10.37% SiO₂, 0.16% TiO₂, 0.15% Fe₂O₃, 0.03% CaO, 0.01%MgO, 0.02% Na₂O₃, and 0.02% K₂O, and has a 9″ outside diameter, a 7.75″inside diameter, and a 14″ depth. A second preferred crucible iscomprised of 99.68% Al₂O₃, 0.07% SiO₂, 0.08% Fe₂O₃, 0.04% CaO, and 0.12%Na₂O₃, and has a 4.5″ outside diameter, a 3.75″ inside diameter and a10″ depth.

Further, the cooling step can alter the results of the process. Suchcooling can include gradual and/or rapid cooling steps. Gradual coolingtypically includes cooling due to heat exchange with air or other gasover 1 to 72 hours, 2 to 50 hours, 3 to 30 hours, or 8 to 72 hours.Rapid cooling, also known as quenching, typically includes an initialcooling with air or other gas to below the solidus temperature, therebyforming a solid mass, and placing the solid mass into a bath comprisinga suitable fluid such as tap water, distilled water, deionized water,other forms of water, gases (as defined above), liquid nitrogen or othersuitable liquified gases, a thermally-stable oil (e.g., silicone oil) ororganic coolant, and combinations thereof. The bath should contain asuitable quantity of liquid at a suitable temperature, such that thedesired amount of cooling occurs. The ingot can be removed from thecrucible before or after completing the cooling. While the material iscooling, the environment can be stirred, mixed or agitated. This can beaccomplished by maintaining a flow of coolant over the material, oragitating the cooling bath or environment. Alternatively, the coolant isnot disturbed or agitated and circulation of the coolant is minimized.

In one embodiment, the material is cooled in a different vessel (coolingor quench chamber). The cooling chamber can be, for example, apolyethylene (or other plastic) container. The ingot can be placeddirectly, or indirectly, into the cooling vessel (e.g., in a vertical orhorizontal orientation). Generally, the ingot can be placed at leastabout 6 inches from the inside wall of the container. The height of thecoolant can be at least about 12 inches above and below the surface ofthe ingot. A refractory material (e.g., a ceramic block rinsed withcoolant (e.g., DI water) and, optionally dried or allowed to dry) may beused to support the ingot in the quench chamber.

Where the material is cooled in a different vessel from the reactor orinduction furnace, the material can be removed, manually or robotically,to a clean, protected surface. This removal may be accomplished manuallyusing a pair of tongs (e.g. cast iron, steel, stainless steel, nickel,titanium, tungsten or other high temperature melting transition metal).Manual removal can also be accomplished by donning heavy, insulated,heat resistant gloves.

Where the crucible is removed from the reactor with the material, thecrucible should be removed before or after cooling. The crucible can beremoved by gently peeling it away from the material. A hammer, ram orwedge can be used to perform this function. However, care should be usedto avoid striking the material hard with the hammer or otherwise causinga substantial impact upon or metal contact with the material. In oneembodiment, the crucible removal can be performed in the presence of airat about 350±75° F., 750±250° F., 1100±250° F., or at T_(solidus) −75°F., T_(solidus) −5° F.

A new composition of matter of the present invention can manifest itselfas a transient, adjustable, or permanent change in energy and/orassociated properties, as broadly defined. Property change can beexhibited as or comprise a change in: (1) structural atomic character(e.g., XES/XRF peak creation, peak fluidity, peak intensity, peakcentroid, peak profile or shape as a function of material/sampleorientation, atomic energy level(s), and TEM, STM, MFM scans); (2)electronic character (e.g., SQUID, scanning SQUID, scanningmagnetoresistive microscopy, scanning magnetic microscope, magnetometer,non-contact MFM, electron electromagnetic interactions, quantum (ortopological) order^(1, 2), quantum entanglement³, Jahn-Teller effect,ground state effects, electromagnetic field position/orientation, energygradients, Hall effect, voltage, capacitance, voltage decay rate,voltage gradient, voltage signature including slope of decay and/orchange of slope decay, voltage magnitude, voltage orientation); (3)structural molecular or atomic character (e.g., SEM, TEM, STM, AFM, LFM,and MFM scans, optical microscopy images, and structural orientation,ordering, long range alignment/ordering, anisotropy); (4) physicalconstants (e.g., color, crystalline form, specific rotation, emissivity,melting point, boiling point, density, refractive index, solubility,hardness, surface tension, dielectric, magnetic susceptibility,coefficient of friction, x-ray wavelengths); (5) physical properties(e.g., mechanical, chemical, electrical, thermal, engineering, and thelike); and (6) other changes that differentiate naturally occurringmaterials from manufactured materials created by inducing a change inmatter.

A preferred analytical method is x-ray fluorescence spectrometry. X-rayfluorescence spectrometry is described in “X-Ray FluorescenceSpectrometry”, by George J. Havrilla in “Handbook of InstrumentalTechniques for Analytical Chemistry,” Frank A. Settle, Ed.,Prentice-Hall, Inc: 1997, which is incorporated herein by reference. XRFspectrometry is a well-known and long-practiced method, which has beenused to detect and quantify or semi-quantify the elemental composition(for elements with Z>11) of solid and liquid samples. This techniquebenefits from minimal sample preparation, wide dynamic range, and beingnondestructive. Typically, XRF data are not dependent on which dimension(e.g., axial or radial) of a sample was analyzed. Accuracy of less than1% error can generally be achieved with XRF spectrometry, and thetechnique can have detection limits of parts per million.

XRF spectrometry first involves exciting an atom, such that an innershell electron is ejected. Upon ejection of an electron, an outer shellelectron will “drop” down into the lower-energy position of the ejectedinner shell electron. When the outer shell electron “drops” into thelower-energy inner shell, x-ray energy is released. Typically, anelectron is ejected from the K, L, or M shell and is replaced by anelectron from the L, M, or N shell. Because there are numerouscombinations of ejections and replacements possible for any givenelement, x-rays of several energies are emitted during a typical XRFexperiment. Therefore, each element in the Periodic Table has a standardpattern of x-ray emissions after being excited by a sufficientlyenergetic source, since each such element has its own characteristicelectronic state. By matching a pattern of emitted x-ray energies tovalues found in tables, such as those on pages 10-233 to 10-271 of“Handbook of Chemistry and Physics, 73^(rd) Edition,” edited by D. R.Lide, CRC Press, 1992, which is incorporated herein by reference, onecan identify which elements are present in a sample. In addition, theintensity of the emitted x-rays allows one to quantify the amount of anelement in a sample.

There are two standard variations of the XRF technique. First, as anenergy-dispersive method (EDXRF), the XRF technique uses a detector suchas a Si(Li) detector, capable of simultaneously measuring the energy andintensity of x-ray photons from an array of elements. EDXRF iswell-suited for rapid acquisition of data to determine gross elementalcomposition. Typically, the detection limits for EDXRF are in the rangeof tens to hundreds of parts-per-million. A wavelength-dispersivetechnique (WDXRF) is generally better-suited for analyses requiring highaccuracy and precision. WDXRF uses a crystal to disperse emitted x-rays,based on Bragg's Law. Natural crystals, such as lithium fluoride andgermanium, are commonly used for high-energy (short wavelength) x-rays,while synthetic crystals are commonly used for low-energy (longerwavelength) x-rays. Crystals are chosen, in part, to achieve desiredresolution, so that x-rays of different energies are dispersed todistinguishable 2θ angles. WDXRF can either measure x-rays sequentially,such that a WDXRF instrument will step through a range of 2θ angles inrecording a spectrum, or there will be detectors positioned at multiple2θ angles, allowing for more rapid analysis of a sample.

Detectors for WDXRF commonly include gas ionization and scintillationdetectors. A further description of the use of WDXRF technique in thepresent invention can be found in Example 1. Results from EDXRF andresults from WDXRF can be compared by determining the relationshipbetween a 2θ angle and the wavelength of the corresponding x-ray (e.g.,using Bragg's Law) and converting the wavelength into energy (e.g.,energy equals the reciprocal of the wavelength multiplied by Planck'sconstant and the velocity of light).

Analysis of emitted x-rays can be carried out automatically orsemi-automatically, such as by using a software package (e.g., UNIQUANT®software, Thermo Fisher Scientific, Inc.) for either EDXRF or WDXRF.UNIQUANT® is used for standard-less, semi-quantitative to quantitativeXRF analysis using the intensities measured by a sequential x-rayspectrometer. The software package unifies all types of samples into oneanalytical program. The UNIQUANT® software program is highly effectivefor analyzing samples for which no standards are available. Samplepreparation is usually minimal or not required at all. Samples can be ofvery different natures, sizes and shapes. Elements from fluorine orsodium up to uranium, or their oxide compounds, can be analyzed insamples such as a piece of glass, a screw, metal drillings, lubricatingoil, loose fly ash powder, polymers, phosphoric acid, thin layers on asubstrate, soil, paint, the year rings of trees, and, in general, thosesamples for which no standards are available. The reporting is in weight% along with an estimated error for each element.

In software packages such as UNIQUANT®, an XRF spectrum is composed ofdata channels. Each data channel corresponds to an energy range andcontains information about the number of x-rays emitted at that energy.The data channels can be combined into one coherent plot to show thenumber or intensity of emitted x-rays versus energy or 2θ angle (the 2θangle is related to the wavelength of an x-ray), such that the plot willshow a series of peaks. An analysis of the peaks by one skilled in theart or the software package can identify the correspondence between theexperimentally-determined peaks and the previously-determined peaks ofindividual elements. For an element, peak location (i.e., the centroidof the peak with respect to energy or 2θ angle), peak profile/shape,peak creation, and peak fluidity would be expected to be essentially thesame, within experimental error, for any sample containing the element.If the same quantity of an element is present in two samples, intensitywill also be essentially the same, excepting experimental error andmatrix effects.

A typical software package is programmed to correlate certain datachannels with the emitted x-rays of elements. Quantification of theintensity of emitted x-rays is accomplished by integrating the XRFspectrum over a number of data channels. Based on the measuredintensities and the previously-compiled data on elements, the softwarepackage will integrate over all data channels, correlate the emittedx-ray intensities, and will then calculate the relative abundance orquantity of elements which appear to be present in a sample, based uponcomparison to the standards. Composition of matter changes produced bythe present invention will generally be characterized by an XRF spectrumthat reports: (1) the presence of an element which was not present inthe starting material and was not added during the process; (2) anincreased amount of an element that was not added to the process in theamount measured; or, (3) a decreased amount of an element that was notremoved during the process in the amount indicated. Examples of (3)include a reduction in identifiable spectra referencing the sum beforenormalization and/or reappearance of an element upon combustion.Products of the present invention can also be characterized by thedifference between XRF Uniquant analysis such as by burning the sample(e.g., LECO analysis), described in more detail below.

A “LECO” analysis is meant to include an analysis conducted by theCS-300 Carbon/Sulfur determinator supplied by a LECO computer. TheCS-300 Carbon/Sulfur determinator is a microprocessor based, softwaredriven instrument for measurement of carbon and sulfur content inmetals, ores, ceramics and other inorganic materials.

Analysis begins by weighing out a sample (1 g nominal) into a ceramiccrucible on a balance. Accelerator material is added, the crucible isplaced on the loading pedestal, and the ANALYZE key is pressed. Furnaceclosure is performed automatically, then the combustion chamber ispurged with oxygen to drive off residual atmospheric gases. Afterpurging, oxygen flow through the system is restored and the inductionfurnace is turned on. The inductive elements of the sample andaccelerator couple with the high frequency field of the furnace. Thepure oxygen environment and the heat generated by this coupling causethe sample to combust. During combustion all elements of the sampleoxidize. Carbon bearing elements are reduced, releasing the carbon,which immediately binds with the oxygen to form CO and CO2, the majoritybeing CO2. Also, sulfur bearing elements are reduced, releasing sulfur,which binds with oxygen to form SO₂.

Sample gases are swept in the carrier stream. Sulfur is measured assulfur dioxide in the first IR cell. A small amount of carbon monoxideis converted to carbon dioxide in the catalytic heater assembly whilesulfur trioxide is removed from the system in a cellulose filter. Carbonis measured as carbon dioxide in the IR cells, as gases flow trough theIR cells.

Ideally, the relative abundances will total 100% prior to normalization.However, for a variety of reasons, such as improper or insufficientcalibration, and/or non-planar sample surface the relative abundanceswill not total 100% prior to normalization. Another reason that therelative abundances of elements do not total 100% prior to normalizationis that a portion of the XRF spectrum falls outside of the data channelsthat the software package correlates with an element (i.e., a portion ofthe XRF spectrum is not recognized as belonging to an element and is notincluded in the relative abundance calculation). In this case, therelative abundances will likely total less than 100% prior tonormalization. Further, the samples will often have anisotropiccharacteristics whereby an axial scan is distinct from a radial scan.Thus, products of the invention may be characterized by an XRF spectrumthat is not recognized by the Uniquant software (e.g., sum of knownconcentrations before normalization is less than 100%) described hereinin an amount, for example, of less than 98%, such as less than 90%, suchas less than 80%. In additional embodiments, the software packagereports or detects one or more elements not detected by other methods orare detected in different quantities.

X-ray emission spectrometry (XES), a technique analogous to XRF, alsoprovides electronic information about elements. In XES, a lower-energysource is used to eject electrons from a sample, such that only thesurface (to several micrometers) of the sample is analyzed. Similar toXRF, a series of peaks is generated, which corresponds to outer shellelectrons replacing ejected inner shell electrons. The peak shape, peakfluidity, peak creation, peak intensity, peak centroid, and peak profileare expected to be essentially the same, within experimental error andmatrix effects, for two samples having the same composition.

Thus, XES analysis of the control standard compared to the atomicallyaltered (i.e., manufactured or tailored) state can also be analyzed.Manufactured copper in the axial direction exhibits similar compositionto natural copper (i.e., 99.98%_(wt)), but radial scans exhibit newpeaks in the region close to naturally occurring S, Cl, and K. Theshifting centroid of the observed peaks from the natural species (i.e.,S, Cl, and K) confirms electronic change in the atomic state of the baseelement. Conventional chemical analysis performed using a LECO (IR)analyzer to detect SO_(X) in the vapor phase post sample combustionconfirmed the absence of sulfur at XES lower detection limits.

Non-contact, magnetic force microscopy image or scanning tunnelingmicroscopy (STM) scan can also confirm the production of a newcomposition of matter or manufactured or tailored material, identifiedby an altered and aligned electromagnetic network. Individually, andfrom differing vantage points, these scans show the outline of thechanged electromagnetic energy network.

New compositions of matter can be electronically modified to induce longrange ordering/alignment. Optical microscopy and SEM imaging of thematerial verifies the degree and extent of long range ordering achieved.

Non-contact, magnetic force microscopy image or scanning tunnelingmicroscopy (STM) scans can also confirm the production of a newcomposition of matter or manufactured or tailored material, identifiedby an altered and aligned electromagnetic network. Individually, andfrom differing vantage points, these scans can show the outline of thechanged electromagnetic energy network. Non-contact MFM imaging can showthat products of the invention often possess clear pattern repetitionand intensity of the manufactured material when compared to the naturalmaterial, or starting material. Products of the invention can becharacterized by the presence of magnetic properties in high purity,non-magnetic metals, such as elemental copper (e.g., 99.98%_(wt)).

Products can also be characterized by color changes. The variation incolor of copper products ranged from black, copper, gold, silver andred. Other visual variations included translucency and near transparencyat regions. While not being bound by theory, the alteration of themetal's electronic state along the continuum enables the new compositionof matter's color to be adjusted along the continuum.

Other products of the processes are characterized by changes inhardness. The variation in diamond pyramid hardness between differentmanufactured copper samples ranged from about 25 to 90 (or 3 to 9 timeshigher than natural copper). Hardness change can be anisotropic.

Manipulation of the electrodynamic components affecting the orientationof a manufactured metal's or alloy's electromagnetic field can enablethe observance of a Hall voltage (V_(H)). Manipulation of theelectrodynamic components enables intensification of electromagneticfield affording charge concentration on the surface of the atoms withinthe bulk as opposed to the bulk surface of the bath. Properties thatreflect field repositioning can include changing capacitance and voltagedecay rate and voltage gradients within a conducting bulk media.

The products produced by the process have utilities readily apparent tothose skilled in the art. Indeed, materials which comprise metals can beused to manufacture products having adjustable chemical properties(e.g., regioselectivity, regiospecificity, or reaction rate), electronicproperties (e.g., band gap, susceptibility, resistivity, or magnetism),mechanical properties (e.g., ductility or hardness) and/or opticalproperties (e.g., color).

The products of this invention are essentially carbon free. In contrast,the products as described in U.S. Pat. No. 7,238,297, for example, arecharacterized by carbon at saturation levels or above. “Essentially freeof carbon”, as defined in this case, means that the product has no morethan the amount of carbon present in the starting material. That is, itis unnecessary to add carbon to the process in order to achievetailoring. The prior art products generally contained carbon in amountsthat equal or exceed saturation. For example, in the case of aluminum,carbon saturation is between approximately 0.22 and 0.71 atomic %. Inthe case of copper, carbon saturation is about 0.04 atomic %. Thus, inone embodiment, the products of the invention are characterized by oneor more electronic and/or physical characteristics described above inaddition to having a carbon percentage less than saturation. In apreferred embodiment, the product has no more than the carbon content ofthe material added to the process. In another embodiment, the product isessentially free of carbon and, in one embodiment, contains nodetectable carbon.

As discussed above, analysis of the composition by X-ray fluorescence isa convenient method for detecting tailoring of a material. Tailoring isdetected if the report generated detects the presence of an element that(1) was not present in the starting material and was not added or (2)was present in the starting material and (a) additional elements was notadded or (b) was not removed or diluted. Thus, in preferred embodiments,the invention relates to compositions, essentially free of carbon,wherein the composition (e.g., a metal, such as copper) comprises amaterial characterized by an X-ray fluorescence analysis report whereinthe report recites the presence of an element in the periodic tablewherein said composition has not been in contact with said element; orcomprises a material characterized by an X-ray fluorescence analysisreport wherein the report recites a concentration of an element in theperiodic table that exceeds the concentration of said element added tothe composition; or comprises a material characterized by an X-rayfluorescence analysis report wherein the report recites a concentrationof an element in the periodic table that is less than the concentrationof said element added to the composition.

Example 1

The object of this run was to duplicate a previously “failed run.” Theprior run “failed” due to insufficient insulating wraps around thecrucible causing a large heat loss an inability to reach the initialsaturation temperature of 2462° F. even after allowing the unit to applymaximum power—40 Kw for three hours. After maintaining full power for 3hours the final temperature reached on run RO14-02-005 was 2300° F. Toduplicate, all insulating wraps were removed from the outside of thecrucible. A cylindrical alumina-based crucible (99.68% Al₂O₃, 0.07%SiO₂, 0.08% Fe₂O₃, 0.04% CaO, 0.12% Na₂O₃; 4.5″ O.D.×3.75″ I.D.×14.5″depth) of a 100-pound induction furnace reactor (Inductotherm) fittedwith a 73-30R Powertrak power supply. The induction coil attached to thepower supply had the following dimensions: 1 foot 3 inch O.D. by 1 foot1 inch I.D. The total coil height was 1 foot 5 inches. The active zoneof the coil comprised 8 active wraps with a total height of 1 foot 1quarter inch. There is a single inactive cooling wrap above and belowthe top and bottom active wraps. The top inactive wrap is 2.249 inchesabove the top active wrap. The bottom inactive wrap is 2.725 inchesbelow the bottom active wrap. The reactor was charged with 9080 g copper(99.98% purity) through its charging port. The reactor was fitted with agraphite cap and a ceramic liner (i.e., the crucible, from EngineeringCeramics). During the entire procedure, a slight positive pressure of100% Ar (˜0.5 psi) was maintained in the reactor using a continuousbackspace purge.

The induction furnace power was then initiated. The reactor wasprogrammed to heat to 2462° F. over a 16.5-hour time frame, at a rate nogreater than 150° F./hr, as limited by the integrity of the crucible.The induction furnace operated in the frequency range of 0 kHz to 3000kHz, with frequency determined by a temperature-controlled feedback loopimplementing an Omega Model CN300 temperature controller. After the16.5-hour heat up, a three-hour hold was programmed in to match theconditions of run RO14-02-005. Again, as in run RO14-02-005, the bathtemperature was unable to reach the saturation temperature of 2462° F.even after applying full power—40 Kw—for three hours. The finaltemperature reached on run RO14-08-004 was 2386° F. FIGS. 1A-1Hillustrates the bath temperature and power during the run. The figuresillustrate the cyclic processing incurred during the initial heating ofthe induction furnace, which was sufficient to tailor the product.

The products of this experiment and the failed experiment referencedherein, were subjected to Uniquant analysis, as described herein. Theresults are set forth in the tables below.

ELC, Inc. ANALYSIS REPORT by Uniquant NEW.683 Spectrometersconfiguration: ARL 8410 Rh 60 kV LiF220 LiF420 Ge111 TlAP Sample ident =14-08-10 TOP AXIAL Further info = 14-08-10 TOP AXIAL VAC Kappa list =15-Nov-94 Calculated as: Elements X-ray path = Vacuum Case number = 0Eff. Diam. = 25.00 mm KnownConc = 0% Rest = 0% Dil/Sample = 0 ViewedMass = 18000.00 mg Sample Height = 5 mm Channel list = 17-Jul-08Spectral impurity data: CAL.950 Film type = No supporting film KnownArea, % Rest, Diluent/Sample and Mass/Area Eff. Area = 490.6 mm2 < meansthat the concentration is <20 ppm <2e means wt % <2 StdErr. The + in Z +El means involved in Sum = 100% Z wt % StdErr Z wt % StdErr Z wt %StdErr SumBe . . . F 0 0.040 29 + Cu 99.86 0.05 51 Sb < 11 + Na < 30 Zn< 52 Te < 12 Mg < 31 Ga <2e 0.003 53 I < 13 Al < 32 Ge < 55 Cs < 14 Si <33 As < 56 Ba < 15 P < 34 Se < SumLa . . . Lu 0.10 0.07 16 + S 0.00550.0005 35 Br < 72 + Hf < 16 So 37 Rb < 73 + Ta < 17 + Cl 0.0058 0.000838 Sr < 74 W < 18 Ar < 39 Y < 75 Re <2e 0.008 19 K < 40 Zr < 76 Os <2e0.007 20 Ca < 41 Nb < 77 + Ir 0.023 0.009 21 Sc < 42 Mo < 78 Pt <2e0.008 22 + Ti 0.007 0.001 44 Ru < 79 Au <2e 0.007 23 V < 45 Rh < 80 Hg <24 + Cr 0.0027 0.0006 46 Pd < 81 Tl < 25 Mn < 47 Ag <2e 0.002 82 Pb < 26Fe < 48 Cd  0.004 0.002 83 Bi < 27 Co < 49 In < 90 Th < 28 Ni < 50 Sn<2e 0.002 92 U < Light Elements Noble Elements Lanthanides  4 Be 44 Ru <57 + La 0.029 0.005  5 B 45 Rh < 58 Ce <  6 C 46 Pd < 59 + Pr 0.0210.003  7 N 47 Ag <2e 0.002 60 Nd <  8 O 75 Re <2e 0.008 62 Sm <2e 0.003 9 F < 76 Os <2e 0.007 63 Eu < 77 + Ir  0.023 0.009 64 Gd < 78 Pt <2e0.008 65 + Tb 0.008 0.002 79 Au <2e 0.007 66 Dy < 67 Ho < 68 + Er 0.0260.003 69 + Tm 0.008 0.004 70 Yb < 71 + Lu <2e 0.014 KnownConc = 0 REST =0 D/S = 0 Sum Conc's before normalisation to 100%: 98.4% NEW.684Spectrometers configuration: ARL 8410 Rh 60 kV LiF220 LiF420 Ge111 TlAPSample ident = 14-08-10 RADIAL Further info = 14-08-10 RADIAL VAC Kappalist = 15-Nov-94 Calculated as: Elements X-ray path = Vacuum Case number= 0 Eff. Diam. = 25.00 mm KnownConc = 0% Rest = 0% Dil/Sample = 0 ViewedMass = 18000.00 mg Sample Height = 5 mm Channel list = 17-Jul-08Spectral impurity data: CAL.950 Film type = No supporting film KnownArea, % Rest, Diluent/Sample and Mass/Area Eff. Area = 490.6 mm2 < meansthat the concentration is <20 ppm <2e means wt % <2 StdErr. The + in Z +El means involved in Sum = 100% Z wt % StdErr Z wt % StdErr Z wt %StdErr SumBe . . . F 0 0.045 29 + Cu 99.87 0.05 51 Sb < 11 Na < 30 Zn <52 Te < 12 Mg < 31 Ga <2e 0.003 53 I < 13 Al < 32 Ge < 55 Cs < 14 Si <33 As < 56 + Ba 0.009 0.003 15 P < 34 Se < SumLa . . . Lu 0.076 0.077 16S 35 Br < 72 + Hf < 16 + So 0.0048 0.0006 37 Rb < 73 + Ta < 17 + Cl0.007 0.001 38 Sr < 74 W < 18 Ar < 39 Y < 75 + Re 0.022 0.009 19 + K0.0020 0.0009 40 Zr < 76 Os < 20 + Ca 0.024 0.002 41 Nb < 77 Ir <2e0.009 21 Sc < 42 Mo <2e 0.003 78 Pt < 22 + Ti 0.007 0.001 44 Ru < 79 Au< 23 V < 45 Rh < 80 Hg <2e 0.007 24 Cr < 46 Pd < 81 Tl < 25 Mn < 47 Ag <82 Pb < 26 Fe < 48 Cd <2e 0.002 83 Bi < 27 Co < 49 In < 90 Th < 28 Ni <50 Sn < 92 U < Light Elements Noble Elements Lanthanides  4 Be 44 Ru <57 + La 0.024 0.006  5 B 45 Rh < 58 Ce <2e 0.002  6 C 46 Pd < 59 + Pr0.008 0.003  7 N 47 Ag < 60 Nd <  8 O 75 + Re  0.022 0.009 62 Sm <2e0.003  9 F < 76 Os < 63 Eu < 77 Ir <2e 0.009 64 Gd < 78 Pt < 65 Tb <2e0.002 79 Au < 66 Dy < 67 Ho < 68 + Er 0.025 0.004 69 Tm < 70 Yb < 71 +Lu <2e 0.014 KnownConc = 0 REST = 0 D/S = 0 Sum Conc's beforenormalisation to 100%: 90.5 JOB.785 Spectrometers configuration: ARL8410 Rh 60 kV LiF220 LiF420 Ge111 TlAP Sample ident = 14-02-05 TOP AXFurther info = 14-02-05 TOP AXIAL UNK VAC Kappa list = 15-Nov-94Calculated as: Elements X-ray path = Vacuum Case number = 0 Eff. Diam. =25.00 mm KnownConc = 0% Rest = 0% Dil/Sample = 0 Viewed Mass = 18000.00mg Sample Height = 5 mm Channel list = 29-Apr-02 Spectral impurity data:CAL.909 Teflon Film type = No supporting film Known Area, % Rest,Diluent/Sample and Mass/Area Eff. Area = 490.6 mm2 < means that theconcentration is <20 ppm <2e means wt % <2 StdErr. The + in Z + El meansinvolved in Sum = 100% Z wt % StdErr Z wt % StdErr Z wt % StdErr SumBe .. . F 0 0.044 29 + Cu 99.21 0.04 51 Sb < 11 + Na 0.036 0.013 30 + Zn <52 Te < 12 Mg < 31 + Ga 0.006 0.003 53 I < 13 + Al 0.31 0.02 32 Ge < 55Cs < 14 + Si 0.35 0.02 33 As < 56 Ba <2e 0.003 15 + P < 34 Se < SumLa .. . Lu 0.027 0.072 16 + S 0.0027 0.0003 35 Br < 72 + Hf < 16 So 37 Rb <73 + Ta < 17 + Cl 0.016 0.001 38 Sr < 74 W < 18 + Ar 0.014 0.001 39 Y <75 Re < 19 K < 40 Zr < 76 Os < 20 Ca < 41 Nb < 77 + Ir 0.023 0.008 21 Sc< 42 Mo <2e 0.002 78 Pt < 22 Ti <2e 0.001 44 Ru < 79 Au < 23 V < 45 Rh<2e 0.002 80 Hg < 24 Cr < 46 Pd < 81 Tl < 25 Mn < 47 Ag < 82 Pb < 26 Fe< 48 Cd < 83 Bi < 27 + Co < 49 In < 90 Th < 28 Ni < 50 Sn < 92 U < LightElements Noble Elements Lanthanides  4 Be 44 Ru < 57 + La 0.011 0.005  5B 45 Rh <2e 0.002 58 Ce <  6 C 46 Pd < 59 Pr <  7 N 47 Ag < 60 Nd <  8 O75 Re < 62 Sm <  9 F < 76 Os < 63 Eu <2e 0.002 77 + Ir  0.023 0.008 64Gd < 78 Pt < 65 Tb < 79 Au < 66 Dy < 67 Ho < 68 + Er 0.012 0.004 69 Tm <70 Yb < 71 + Lu < KnownConc = 0 REST = 0 D/S = 0 Sum Conc's beforenormalisation to 100%: 98.4% JOB.786 Spectrometers configuration: ARL8410 Rh 60 kV LiF220 LiF420 Ge111 TlAP Sample ident = 14-02-05 RADFurther info = 14-02-05 RAD UNK VAC Kappa list = 15-Nov-94 Calculatedas: Elements X-ray path = Vacuum Case number = 0 Eff. Diam. = 25.00 mmKnownConc = 0% Rest = 0% Dil/Sample = 0 Viewed Mass = 18000.00 mg SampleHeight = 5 mm Channel list = 29-Apr-02 Spectral impurity data: CAL.909Teflon Film type = No supporting film Known Area, % Rest, Diluent/Sampleand Mass/Area Eff. Area = 490.6 mm2 < means that the concentration is<20 ppm <2e means wt % <2 StdErr. The + in Z + El means involved in Sum= 100% Z wt % StdErr Z wt % StdErr Z wt % StdErr SumBe . . . F 0 0.04229 + Cu 99.23 0.04 51 Sb < 11 + Na 0.066 0.012 30 + Zn < 52 Te < 12 Mg <31 Ga <2e 0.003 53 I < 13 + Al 0.42 0.02 32 Ge < 55 Cs < 14 + Si 0.190.01 33 As < 56 Ba < 15 + P < 34 Se < SumLa . . . Lu 0.012 0.073 16 S 35Br < 72 + Hf < 16 + So 0.0046 0.0004 37 Rb < 73 + Ta < 17 + Cl 0.0310.003 38 Sr < 74 W < 18 + Ar 0.014 0.001 39 Y < 75 Re < 19 + K 0.00450.0008 40 + Zr 0.0041 0.0010 76 Os < 20 + Ca 0.0065 0.0009 41 Nb < 77 +Ir 0.024 0.008 21 Sc < 42 Mo <2e 0.002 78 Pt < 22 Ti <2e 0.001 44 Ru <79 Au < 23 V < 45 Rh < 80 Hg <2e 0.006 24 Cr < 46 Pd < 81 Tl <2e 0.00525 Mn < 47 Ag <2e 0.002 82 Pb < 26 Fe < 48 Cd < 83 Bi < 27 Co < 49 In <90 Th < 28 Ni < 50 Sn < 92 U < Light Elements Noble Elements Lanthanides 4 Be 44 Ru < 57 La <2e 0.005  5 B 45 Rh < 58 Ce <  6 C 46 Pd < 59 Pr < 7 N 47 Ag <2e 0.002 60 Nd <  8 O 75 Re < 62 Sm <  9 F < 76 Os < 63 Eu <77 + Ir 0.024 0.008 64 Gd < 78 Pt < 65 + Tb 0.005 0.002 79 Au < 66 Dy <67 Ho < 68 Er < 69 Tm < 70 Yb < 71 + Lu < KnownConc = 0 REST = 0 D/S = 0Sum Conc's before normalisation to 100%: 98.8% NEW.685 Spectrometersconfiguration: ARL 8410 Rh 60 kV LiF220 LiF420 Ge111 TlAP Sample ident =14-08-04 AXIAL Further info = 14-08-04 TOP AXIAL VAC Kappa list =15-Nov-94 Calculated as: Elements X-ray path = Vacuum Case number = 0Eff. Diam. = 25.00 mm KnownConc = 0% Rest = 0% Dil/Sample = 0 ViewedMass = 18000.00 mg Sample Height = 5 mm Channel list = 17-Jul-08Spectral impurity data: CAL.950 Film type = No supporting film KnownArea, % Rest, Diluent/Sample and Mass/Area Eff. Area = 490.6 mm2 < meansthat the concentration is <20 ppm <2e means wt % <2 StdErr. The + in Z +El means involved in Sum = 100% Z wt % StdErr Z wt % StdErr Z wt %StdErr SumBe . . . F 0 0.042 29 + Cu 99.96 0.05 51 Sb < 11 Na < 30 Zn <52 Te < 12 Mg < 31 Ga <2e 0.003 53 I < 13 Al < 32 Ge < 55 Cs <2e 0.00314 Si < 33 As < 56 + Ba 0.006 0.003 15 P < 34 Se < SumLa . . . Lu 0.0230.077 16 S < 35 Br < 72 + Hf < 16 So 37 Rb < 73 + Ta < 17 Cl < 38 Sr <74 W < 18 Ar < 39 Y < 75 Re <2e 0.008 19 + K 0.0027 0.0010 40 Zr < 76 Os< 20 Ca <2e 0.002 41 Nb < 77 Ir <2e 0.009 21 Sc < 42 Mo < 78 Pt <2e0.008 22 Ti <2e 0.002 44 Ru < 79 Au <2e 0.007 23 V < 45 Rh < 80 Hg < 24Cr < 46 Pd < 81 + Tl 0.012 0.005 25 Mn < 47 Ag < 82 Pb < 26 Fe < 48 Cd <83 Bi < 27 Co < 49 In < 90 Th < 28 Ni < 50 Sn < 92 U < Light ElementsNoble Elements Lanthanides  4 Be 44 Ru < 57 La <  5 B 45 Rh < 58 Ce <  6C 46 Pd < 59 Pr <  7 N 47 Ag < 60 Nd <  8 O 75 Re <2e 0.008 62 Sm <  9 F< 76 Os < 63 Eu < 77 Ir <2e 0.009 64 Gd < 78 Pt <2e 0.008 65 Tb < 79 Au<2e 0.007 66 Dy < 67 Ho < 68 + Er 0.017 0.004 69 Tm < 70 Yb < 71 + Lu<2e 0.014 KnownConc = 0 REST = 0 D/S = 0 Sum Conc's before normalisationto 100%: 99.0% NEW.686 Spectrometers configuration: ARL 8410 Rh 60 kVLiF220 LiF420 Ge111 TlAP Sample ident = 14-08-04 RADIAL Further info =14-08-04 RADIAL VAC Kappa list = 15-Nov-94 Calculated as: Elements X-raypath = Vacuum Case number = 0 Eff. Diam. = 25.00 mm KnownConc = 0% Rest= 0% Dil/Sample = 0 Viewed Mass = 18000.00 mg Sample Height = 5 mmChannel list = 17-Jul-08 Spectral impurity data: CAL.950 Film type = Nosupporting film Known Area, % Rest, Diluent/Sample and Mass/Area Eff.Area = 490.6 mm2 < means that the concentration is <20 ppm <2e means wt% <2 StdErr. The + in Z + El means involved in Sum = 100% Z wt % StdErrZ wt % StdErr Z wt % StdErr SumBe . . . F 0 0.043 29 + Cu 99.88 0.05 51Sb < 11 + Na <2e 0.014 30 Zn < 52 Te < 12 Mg < 31 + Ga  0.010 0.003 53 I< 13 Al < 32 Ge <2e 0.003 55 Cs < 14 Si < 33 As < 56 + Ba 0.008 0.003 15P < 34 Se < SumLa . . . Lu 0.065 0.076 16 + S < 35 Br < 72 + Hf <2e0.023 16 So 37 Rb < 73 + Ta < 17 + Cl 0.018 0.002 38 Sr < 74 W < 18 Ar <39 Y < 75 Re <2e 0.009 19 K < 40 Zr < 76 Os <2e 0.008 20 + Ca 0.00770.0010 41 Nb < 77 + Ir 0.022 0.008 21 Sc < 42 Mo < 78 Pt <2e 0.008 22 Ti< 44 Ru < 79 Au < 23 V < 45 Rh < 80 Hg <2e 0.007 24 + Cr < 46 Pd < 81 Tl< 25 Mn < 47 Ag < 82 Pb <2e 0.003 26 Fe < 48 Cd < 83 Bi < 27 Co < 49 In< 90 Th <2e 0.003 28 Ni < 50 Sn < 92 U < Light Elements Noble ElementsLanthanides  4 Be 44 Ru < 57 La <2e 0.007  5 B 45 Rh < 58 Ce <2e 0.002 6 C 46 Pd < 59 + Pr 0.022 0.002  7 N 47 Ag < 60 Nd <  8 O 75 Re <2e0.009 62 Sm <  9 F < 76 Os <2e 0.008 63 Eu < 77 + Ir  0.022 0.008 64 Gd< 78 Pt <2e 0.008 65 + Tb 0.004 0.002 79 Au < 66 Dy < 67 Ho < 68 + Er0.018 0.004 69 + Tm <2e 0.004 70 Yb < 71 + Lu < KnownConc = 0 REST = 0D/S = 0 Sum Conc's before normalisation to 100%: 94.6%

While this invention has been particularly shown and described withreferences to preferred embodiments thereof, it will be understood bythose skilled in the art that various changes in form and details may bemade therein without departing from the scope of the inventionencompassed by the appended claims.

What is claimed is:
 1. A method of processing a material, comprising thesteps of: (A) adding and optionally melting a material in a reactor; (B)subjecting the material to an iterative cycling of increasing anddecreasing the temperature of the material, such as by varying thetemperature of the material between two temperatures over one or morecycles, in the substantial absence of carbon, optionally in the presenceof an inert gas flow through the material; (C) optionally repeating step(B) at the same or different temperatures, one of said temperatures ispreferably greater than at least one or both of the temperatures of step(B); and (D) optionally, cooling the material obtained from step (B) or(C) and selecting a tailored material.
 2. The method of claim 1, whereinthe material is essentially carbon free.
 3. The method of claim 1,wherein the material is a metal, such as a transition metal.
 4. Themethod of claim 2, wherein the transition metal is chromium, manganese,iron, cobalt, nickel, copper, zinc, or alloys thereof.
 5. The method ofclaim 1, wherein an the inert gas is added during step (B) and/or step(C) and is selected from one or more of argon, nitrogen, helium, neon,xenon, hydrogen, krypton, and mixtures thereof.
 6. The method of claim1, wherein the method comprises at least one of the following: (a) a gasor gaseous addition (e.g., nitrogen, hydrogen, and/or noble gas) isadded to the material through a lance set at a level above the liquidlevel; (b) at least one of the gases or gaseous additions comprises agas mixture; (c) at least one of the gases has been exposed toradiation; (d) current, e.g., AC or DC current, is added to the materialin a further step or during one or more of the above steps; (e) duringthe cooling step, a gas is added to the material; and/or (f) during thecooling step, the material is quenched with water wherein the water isnot stirred; (g) at least one form of radiation has been filtered; (h)the material is exposed to radiation in a further step or during one ormore of the above steps; and/or (i) varying the reactor power (e.g.,above normal holding power) between two power levels over ½, one or morecycles.
 7. A tailored material produced by the process of claim
 1. 8. Acomposition comprising a material characterized by an X-ray fluorescenceanalysis report wherein the report recites the presence of an element inthe periodic table wherein said composition has not been in contact withsaid element and is essentially free of carbon.
 9. The composition ofclaim 8, wherein the material comprises a metal.
 10. The composition ofclaim 8, wherein the material comprises copper.
 11. A compositioncomprising a material characterized by an X-ray fluorescence analysisreport wherein the report recites a concentration of an element in theperiodic table that exceeds the concentration of said element added tothe composition and is essentially free of carbon.
 12. The compositionof claim 11, wherein the material comprises a metal.
 13. The compositionof claim 11, wherein the material comprises copper.
 14. A compositioncomprising a material characterized by an X-ray fluorescence analysisreport wherein the report recites a concentration of an element in theperiodic table that is less than the concentration of said element addedto the composition and is essentially free of carbon.
 15. Thecomposition of claim 14, wherein the material comprises a metal.
 16. Thecomposition of claim 14, wherein the material comprises copper.